United States Patent [191 [11] Patent Number: 4,816,038 Koch et al. [45] Date of Patent: Mar. 28, 1989

[54] METAL COMPLEXES OF MANNICH BASES 3,877,889 4/1975 Dix ........................................ .. 44/73

WITH A SCI-EFF B ASE 3,945,933 3/1976 Chibnik et a1. ...... .. ‘ 3,988,323 10/1976 L’Eplattenier et al.

[75] Inventors: Frederick W. Koch, wiiloughby 4,029,683 6/1977 Aratani et a1. ............. .. 260/438 1 Hills; Gail A. Evans Euclid; Casper 4,044,036 8/1977 Han et a1. .... .. 260/4381 J. Dorer, Jr., Lyndliurst, all of Ohio; 4,093,614 6/ 1978 Chibnik et al. 260/299 Alan A. De] PaggiO, Houston’ Tex Ct 31. ............... .. R

[73] Assignee: The Lubrizol Corporation, Wickliffe, FOREIGN PATENT DOCUMENTS Ohm 2443017 3/ 1975 Fed. Rep. of Germany .

[21] Appl' NOJ 159,100 794015 1/1981 U.S.S.R. .

[22] Filed: Feb. 23, 1988 Primary Examiner-William R. Dixon, Jr. Assistant Examiner-Ellen McAvoy

Related US, Application Data Attorney, Agent, or Firm-James L. Cordek; Joseph P. [63] Continuation-impart of Ser. No. 779,725, Sep. 24, 1985, Escher; R°bert A‘ Franks

abandoned. [57] ABSTRACT

[51] Int. Cl.‘ ......................... .. C10L 1/18; ClOL l/22 Metal complexes of hydroxyl_ and/or thioLcontaining [52] US. Cl. ......................................... .. 44/ 68; 44/ 73; Mannich are prepared by reacting a transition metal_

F 1 ‘1556/32; 556113; 655362/13133 containing agent with an aromatic Mannich. The Man [58] ‘e d of Sea" """""""" " / ’ g 5 6 /1/1 0 ’ 113’ nich is prepared from a substituted hydroxyl- and/or

’ thiol-containing aromatic, an aldehyde or ketone, and a [56] References Cited hydroxyl- and/or thiol-containing amine compound. A

as PATENT DOCUMENTS Schiff hase is then reacted therewith. The products are . _ useful in reducing soot ignition temperatures in diesel

3,169,988 2/ 1965 Luvisi ................................... .. 44/73 particulate traps_ 3,574,837 4/ 1971 Pacheco et a1. 424/248 3,649,659 3/1972 Otto et a1. ............................. .. 44/68

3,875,200 4/ 1975 L’Epiattenier et a1. ...... .. 260/439 R 23 Claims, N0 Drawings

4,816,038 '1 2

METAL COMPLEXES 0F MANNICH BASES DEscRlpTllggil‘égglafEaglgEFERRED WITH A SCHIFF BASE

This is a continuation-in-part of copending applica- 5 tion(s) Ser. No. 779,725 ?led on Sept. 24, 1985, aban— doned.

FIELD OF THE INVENTION

The present invention relates to metal reaction prod nets of Mannich type compounds which generally do not degrade fuels and yet reduce the ignition tempera ture of soot as in a diesel particulate trap.

BACKGROUND 15

German Pat. No. 2,443,017 and corresponding U.S. Pat. No. 4,044,036 relate to one-to-one metal complexes of bis-azomethines which are useful as pigments.

Russian Pat. No. 794,015 relates to copper chelate aqua-complexes suitable as antioxidants for synthetic ester-type lubricating oils. The chelates are obtained by the reaction of the corresponding phenol Mannich base with acopper acetate in a basic medium in methyl alco hol at room temperature.

U.S. Pat. No. 3,574,837 to Pacheco et al relates to Schiff bases which are useful as fungicides.

U.S. Pat. No. 3,875,200 to L’Eplattenier et al relates to bis-azomethine pigments. I

U.S. Pat. No. 3,945,933 to Chibnik et al relates to a multiple metal salt complex of an organic-substituted nitrogenous compound which can be prepared by react ing an organic compound, a polyamine containing at least two nitrogen atoms and at least two metal com pounds, at least one of which is a salt capable of forming a complex with the polyamine and also capable of form ing a complex with said second metal compound.

U.S. Pat. No. 3,988,323 to L’Eplattenier relates to 1:1 and 2:1 metal complexes of bis-hydrazides which are useful as pigments for high molecular weight organic materials.

U.S. Pat. No. 4,029,683 to Arantani et al relates to a process for producing an optically active alkyl chrysan themate wherein 2,5-dimethyl-2,4-hexadiene is reacted with an alkyl diazoacetate in the presence of a copper complex coordinated with a Schiff base.

U.S. Pat. No. 4,044,036 to Hari et a1 relates to 1:1 metal complexes of bis-azomethines.

U.S. Pat. No. 4,093,614 to Chibnik et al relates to a multiple metal salt complex of an organic-substituted nitrogenous compound which can be prepared by react ing an organic compound, an amine containing at least two nitrogen atoms and at least two metal compounds, at least one said metal being a salt capable of forming a coordinated complex of the Werner-type with the amine and also capable of forming a complex with the said second metal compound.

SUMMARY OF THE INVENTION

Compounds useful as distillate fuel additives are pro duced by the reaction product of a hydroxyl- and/or thiol-containing aromatic, an aldehyde or ketone, and a hydroxyl- and/or thiol-containing amine and at least one transition metal-containing agent. This product is then reacted with a Schiff base.

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The (A) hydrocarbyl-substituted hydroxyl- and/or thiol-containing aromatic compound of the present in vention generally has the formula

where Ar is an aromatic groups such as phenyl or poly aromatic group such as naphthyl, and the like. More over, Ar can be coupled aromatic compounds such as naphthyl, phenyl, etc., wherein the coupling agent is O, S, CH2, a lower alkylene group having from 1 to about 6 carbon atoms, NH, and the like with R1 and XH gen erally being pendant from each aromatic group. Exam ples of speci?c coupled aromatic compounds include diphenyl amine, diphenyl methylene and the like. The number of “m” XH groups is usually from 1 to 3, desir ably l or 2, with 1 being preferred. The number of “n” substituted Rl groups is usually from 1 to 4, desirably l or 2 with a single-substituted group being preferred. X is O and/or S with 0 being preferred. That is, if m is 2, X can be both 0, both S, or one 0 and one S. R1 can be a hydrogen or a hydrocarbyl-based substitute having from 1 to about 28 carbon atoms. As used herein and throughout this speci?cation, the term “hydrocarbyl based substituent” or “hydrocarbyl” denotes a substitu ent having a carbon atom directly attached to the re mainder of the molecule and having predominantly hydrocarbyl character within the context of this inven tion. Such substituents include the following:

1. Hydrocarbon substituents, that is, aliphatic (for example alkyl or alkenyl), alicyclic (for example cyclo alkyl or cycloalkenyl) substituents, aromatic-, aliphatic and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form n alicyc lic radical).

2. Substituted hydrocarbon substituents, that is, those containing non-hydrocarbon radicals which, in the con text of this invention, do not alter the predominantly hydrocarbyl character of the substituent. Those skilled in the art will be aware of suitable radicals (e.g., halo, (especially chloro and ?uoro), alkoxyl, mercapto, alkyl mercapto, nitro, nitroso, sulfoxy, etc.).

3. Hetero substituents, that is, substituents which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms. R1 is hydrogen, or said hydrocarbyl from 1 to about

28 carbon atoms such as an alkyl, or an alkyl having from 1 to about 25 carbon atoms, more desirably from about 7 to about 20 carbon atoms, an alkenyl having 2 to about 25 carbon atoms, more desirably from about 8 to about 20 carbon atoms, a cycloalkyl having from 4 to about 10 carbon atoms, more desirably from about 5 to about 7 carbon atoms, an aromatic groups having from about 6 to about 24 carbon atoms, an aromatic-sub stituted alkyl or alkyl-substituted aromatic having a total of from about 7 to about 25 carbon atoms and more desirably from about 7 to about 12 carbon atoms. The hydrocarbon-based substituent preferably is an alkyl having from 7 to about 20 carbon atoms with from

4,816,038 3

about 7 to about 14 carbon atoms being highly pre ferred. Examples of suitable hydrocarbyl-substituted hydroxyl-containing aromatics include the various naphthols, and more preferably the various alkyl-sub stituted cathechols, resorcinols, and hydroquinones, the various xylenols, the various cresols, aminophenols, and the like. Examples of various suitable (A) compounds include heptylphenol, octylphenol, nonylphenol, decyl phenol, dodecylphenol, tetrapropylphenol, and the like. Dodecylphenol, tetrapropylphenol and heptylphenol are especially preferred. Examples of suitable hydrocar byl-substituted thiol-containing aromatics include hep tylthiophenol, octylthiophenol, nonylthiophenol, dode cylthiophenol, tetrapropylthiophenol, and the like. Ex~ amples of suitable thiol- and hydroxyl-containing aro matics include dodecylmonothioresorcinol, Z-mercap toalkylphenol where the alkyl group is as set forth above. R° is H, an amino group or a carboxyl group with H being preferred. The (B) compound of the present invention has the

formula

or a precursor thereof. R2 and R3, independently, can be hydrogen, a hydrocarbon such as an alkyl having from 1 to 18 carbon atoms and more preferably 1 or 2 carbon atoms. The hydrocarbon can also be a phenyl- or an alkyl-substituted phenyl having from about 1 to about 18 carbon atoms and more preferably from about 1 to about 12 carbon atoms. Additionally, R3 can be a car bonyl or a carboxyl-containing hydrocarbon where the hydrocarbon is as described immediately above. Exam ples of suitable (B) compounds include the various alde hydes and ketones such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benz aldehyde, and the like, as well as methyl ethyl ketone, dimethyl ketone, ethyl propyl ketone, butyl methyl ketone, glyoxal, glyoxylic acid and the like. Precursors of such compounds which react as aldehydes under reaction conditions of the present invention can also be utilized and include paraformaldehyde, trioxane, forma lin and the like. Formaldehyde and its polymers, for example, paraformaldehyde are preferred. Nautrally, mixtures of the various (B) reactants can be utilized.

It is an important aspect of the present invention to utilize a (C) hydroxyl- and/or thiol-containing amine compound wiht the hydroxyl-containing compound being preferred. The amino group is desirably a primary amine or a secondary amine. Generally, the thiol- and /or hydroxyl-containing amine compound has from about 1 to about 10 primary or secondary amine groups therein from about 1 to about 10 thiol groups therein, and from about 1 to about 10 hydroxyl groups therein. Desirably, such a compound contains one or two amine groups as well as one or two thiol groups and one or two hydroxyl groups therein. Representative examples of thiol-containing amine compounds include 2-mercap toethyl amine, N-(2-mercaptoethyl)ethanol amine and the like. The preferred hydroxyl-containing amine compound

can be a cyclohydrocarbyl hydroxyl-containing amine, a compound having the formula

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4 or a compound having the formula

The cyclohydrocarbyl compound can contain from 1 to 10 hydroxyl groups, and preferably one or two. De sirably the hydroxyl group is pendant from the ring structure. The number of amino groups is from about 1 to about 10 with one amino group being preferred. The amino group is also desirably pendant from the ring structure. The number of carbon atoms in the cyclohy drocarbyl group is from 3 to 30, with a cycloalkyl hav ing from 3 to 6 being preferred. Examples of such cy clohydrocarbyl hydroxyl-containing amines include Z-aminocyclohexanol and the like.

In the compound having the formula

R4 is a hydrocarbylene having from 1 to 20 carbon atoms. R4 can be linear, branches, and the like. Desir ably, R4 is an alkylene having from 2 to about 6 carbon atoms, and preferably has 2 or 3 carbon atoms.

Considering R5 of the formula

it is hydrogen or a hydrocarbyl having from 1 to about 20 carbon atoms. R5 can be linear, branched, or the like. Desirably, R5 is alkyl having from 1 to about 20 carbon atoms and more desirably from 1 to about 2 carbon .atoms. Preferably, R5 is a hydrogen atom.

The number of repeating units, that is “o” is l to 10 with 1 being preferred. R6 is a hydrogen atom, a hy droxyl-containing hydrocarbyl primary amino group having from 1 to about 20 carbon atoms or a hydro carbyl polyamino group having from 1 to about 20 carbon atoms. Desirably, the hydroxyl-containing hy drocarbyl group is an alkyl containing from 1 to 20 carbon atoms, desirably 2 or 3 carbon atoms with 2 carbon atoms being preferred. Desirably, the hydrocar byl-containing amino group is an alkyl amino groups such as a primary amino group containing from 1 to 20 carbon atoms, more desirably 2 or 3 carbon atoms with 2 carbon atoms being preferred. The hydrocarbyl-con taining polyamino group desirably is an alkyl group containing from 1 to 20 carbon atoms, more desirably 2 or 3 carbon atoms with 2 carbon atoms preferred. This compound can contain a total of 1 to 10 amino groups with 1 or 2 amino groups being preferred. Taken to gether, R5 and R6 has a total number of 24 carbon atoms or less. Examples of said (C) hydroxyl-containing amine

compunds include both mono- and polyamines pro vided that they contain at least one primary or second ary amino group. Examples of speci?c hydroxyl-con taining amines include ethanolamine, di-(3-hydroxy propyl)amine, 3-hydroxybutylamine, 4-hydroxybutyla mine, diethanolamine, di-(2-hydroxypropyl)amine, N (hydroxypropyl)propylamine, N-(2-hydroxyethyl)cy~ clohexylamine, 3-hydroxycyclopentylamine, N hydroxyethyl piperazine, and the like. Examples of suitable amino alcohols include the N-(hydroxy-lower alkyl)amines and polyamines such as 2-hydroxyethyla

4,816,038 5

mine, di-(2-hydroxyethyl)amine, and N,N,N'-tri-(2 hydroxyethyl)ethylenediamine. Also contemplated are other mono- and poly-N

hydroxy alkyl-substituted alkylene polyamines; espe cially those containing 2 to 3 carbon atoms in the alkyl ene radicals and alkylene polyamines containing up to 7 amino groups such as the reaction product of about 2 moles of alkylene oxide and 1 mole of diethylenetri amine. Amino alcohols containing primary amines as set

forth in the above formula containing R4 are described in U.S. Pat. No. 3,576,743 and is hereby fully incorpo rated by reference. Speci?c examples of hyroxy-sub stituted primary amines include Z-amino-l-butanol, 2 amino-2-methyl-l-propanol, 2-amino-1-propanol, 3 amino-l-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethy1-1,3-propanediol, N—(beta-hydroxy propyl)-N’-beta-aminoethy1)piperazine, tris(hydrox ymethy1)amino methane (also known as trisme thylolaminomethane), 2-amino-l-butynol, ethanol amine, beta-(beta-hydroxyethoxy)-ethylamine, gluca mine, glucosamine, 4-amino-3-hydroxy-3-methyl-1 butene (which can be prepared according to procedures known in the art by reacting isoprene oxide with ammo nia, N-(3-aminopropyl)-4-(2-hydroxyethyl)-piperazine, Z-amino-6-methyl-6—heptanol, S-amino-l-pentanol, N (beta-hydroxyethyl)-1,3-diaminopropane, 1,3-diamino Z-hydroxy-propane, N-(beta-hydroxy ethoxyethyl) ethylenediamine, and the like. For further description of the hydroxy-substituted primary amines contemplated as being useful as (C), US. Pat. No. 3,576,743 is ex pressly incorporated herein by reference for its disclo sure of such amines. The (D) agent of the present invention contains a

transition metal, that is, a metal found in Cols. 1B, 2B, 58 through 7B, and Col. 8 of the Periodic Table as set forth in The Handbook of Chemistry and Physics, 61st Edition, CRC Press, Inc., 1980-1981. Any salt of a transition metal can be utilized. Thus, salts of carbon ates, sulfates, nitrates, halogens as for example chlo rides, oxides, hydroxides, combinations thereof and the like can be utilized. Such salts are known to the art as well as to the literature. Desirable transition metals include copper, iron, zinc and manganese. Additionally, various oil-soluble salts can be utilized such as those derived from naphthenates and various carboxylates. That is, the salts can be derived from the reaction of the transition metals with soaps or fatty acids, saturated or unsaturated. The fatty acids generally have from about 8 to about 18 carbon atoms. An additional salt are the metal esters wherein the esters are lower aliphatic and desirably lower alkyl having from about 1 to about 7 carbon atoms. Examples of speci?c transition metals containing salts include zinc oxide, basic copper carbon ate (also referred to as copper hydroxy carbonate), copper acetate, copper bromide, copper butyrate, cop per chloride, copper nitrate, copper oxide, copper pal mitate, copper sulfate, iron acetate, iron bromide, iron carbonate, iron chloride, iron hydroxide, iron nitrate, iron sulfate, manganese acetate, manganese bromide, manganese chloride, manganese sulfate, and the like. Preferred (D) agents include basic copper carbonate and copper acetate. The preparation of the metal complexes of hydroxyl

containing Mannich compounds can be carried out by a variety of methods such as in a single pot or a two-pot preparation. The one-pot method brie?y relates to add ing the (A) hydroxyl-containing aromatic compound,

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6 the (B) saturated aldehyde or ketone, and (C) the hy droxyl- and/or thiol-containing amine compound to a suitable vessel and heating to carry out the'reaction. Reaction temperatures from about ambient to about the decompostion temperature of the Mannich can be uti lized. During reaction, water is drawn off as by sparg ing. Desirably, the reaction is carred out in solvent such as an aromatic-type oil. The amount of the various reac~ tants utilized is desirably on a mole-to-mole basis of (A) and (B) for each (C) secondary amino group or on a two-mole basis of (A) and (B) for each (C) primary amino group, although larger or smaller amounts can also be utilized as set forth hereinbelow. The (D) com pound containing at least one transition metal is then added, typically in a slow manner since the reaction may be exothermic as well as to control foaming. The reaction by-products such as carbon dioxide and water are removed via suitable procedure such as sparging, usually at a temperature greater than the boiling water. However, the temperature is usually less than 150° C. inasmuch as the metal complex formed may be unstable at higher temperatures. The “two-pot” method is basically as set forth below

although various modi?cations thereof can be prac ticed. The hydroxy-containing aromatic compound (A) and the hydroxyl- and/or thiol-containing amine com pound (C) are added to a reaction vessel. The aldehyde or ketone (B) is generally rapidly added and the exo thermic reaction generated is supplemented by mild heat such that the reaction temperature is from about 60° C. to about 90° C. Desirably, the addition tempera ture is less than the boiling point of water, otherwise, the water will bubble off and cause processing prob lems. After the reaction is essentially complete, the water by-product is removed in any conventional man ner as by evaporation thereof which can be achieved by applying a vacuum, applying a sparge, heating or the like. A nitrogen sparge is often utilized at a temperature of from about 100° C. to about 130° C. Naturally, higher or lower temperatures can be utilized. The reaction is generally carried out in a solvent.

Any conventional solvent can be utilized such as tolu ene, xylene or propanol. Often times various oils are utilized such as an aromatic type oil, 100 neutral oil, etc. The amount of the various (A), (B) and (C) compo

nents is as set forth above. However, it is to be under stood that larger or smaller amounts can be utilized. For example, for each primary amino group of (C) from about 0.5 to about 6 moles of (A) and (B) can be utilized and more desirably from about 1.8 to about 2.2 moles of (A) and (B). For each secondary amino group of (C), from about 0.2 to about 2 moles of (A) and (B) can be utilized and more desirably from about 0.9 to about 1.1 moles of (A) and (B). The next step is the reaction of at least one transition

metal containing agent (D) to form a Mannich complex. Desirably, a promoter is utilized in association with the metal-containing compound to free the metal so that it can react with the above reaction product. The pro moteralternatively can'be added before or after the metal addition. Since the formation of the metal com plex may be exothermic, the metal-containing com pound is generally added in a slow manner, for example, dropwise, to control foaming produced by the evolu tion of carbon dioxide as well as the formation of water. Alternatively, the metal-containing compound and the promoter can be mixed in an appropriate solvent and the Mannich complexing material can then be added to

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this mixture. Generally this reaction step is carried out at a temperature of from about room temperature to about 90° C. After sufficient time has elapsed such that the reaciton is generally complete, water and any re maining carbon dioxide is removed by conventional methods such as by sparging at temperatures below that which renders the metal complex unstable. The unstable temperature of the various metal complexes will vary depending upon the type of compound with a guideline being appoximately 150° C. Thus, sparging is generally kept below 130° C. and often under 120° C. As noted above, promoters are often desirable to

improve the rate of reaction of the metal-containing compound. A basic promoter is desirable such as ammo nium hydroxide. Generally, any conventional aqueous basic salt can be utilized which is known to the art and the literature with speci?c examples being ‘potassium hydroxide, sodium hydroxide, sodium carbonate, and the like with ammonium hydroxide being preferred. The amount of promoter generally varies with regard to the type of metal as known to those skilled in the art. The metal complex Mannich compounds of the pres

ent invention generally do not degrade fuels and hence can be utilized in many applications. A particularly suitable use is as a diesel fuel additive. Upon utilization, that is, during combustion, all the organic portions of the metal complex Mannich compound are essentially burned. The remaining metal portion of the compound has been found to reduce the ignition temperature of soot. Thus, soot is much more readily broken down or reacted at lower temperatures as in a particulate soot trap which is often utilized in association with diesel engines. The ?nal step is the reaction of a Schiff base (E) with

the above metal Mannich complex. The use of Schiff bases are desirable in that they help complex or chelate various metals such as copper. A desirable type of a Schiff base utilizing the present

invention is set forth by the following formula

R10 a l (R ), N=C

R8 can be hydrogen or a hydrocarbyl having from 1 to about 20 carbon atoms such‘ as an alkyl having from 1 to 20 carbon atoms with hydrogen or methyl being pre ferred. R8 can also be an alkyl amine, diamine, or poly amine, having from 1 to about 20 carbon atoms open chain or cyclic and up to 7 nitrogen atoms, or an aro matic such as phenyl, naphthyl, etc., or an alkyl-sub stituted aromatic having a total number of from about 6 to about 36 carbon atoms with from about 6 to about 12 carbon atoms being preferred. The number of such R8 groups, that is, p, is 1 or 2 with 1 such group being preferred. Similarly, the number of hydroxyl groups as represented by r is 1 or 2 with 1 such group being pre ferred. R9, independently, can be a hydrogen or a hy drocarbyl having from 1 to 20 carbon atoms such as an alkyl having from 1 to 20 carbon atoms, desirably an alkyl having from 1 to 6 carbon atoms with hydrogen being preferred. R9 can also be an aromatic or an alkyl substituted aromatic having a total number of from 6 to about 36 carbon atoms and desirably from 6 to about 12 carbon atoms therein. The number of such R9 groups, that is sis l or 2 with 1 such group being preferred. R10

(OH) (119).’ I

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8 is hydrogen or a lower alkyl, that is, having from 1 to about 8 carbon atoms, with hydrogen being preferred. The number of groups within the Schiff base is repre sented by t is from 1 to 6 with 2 such groups being preferred. Representative examples of such Schiff bases include N-N’-disalicylidene-1,2-propanediamine, N salicylideneaniline, N,N’-disalicylideneethylenedia mine, salicylal-beta-N-aminoethylpiperazine and the like. The amount of said Schiff base is from about i to

about 4 gram atoms of nitrogen as imine groups per gram atom of said metal in said reaction product and more desirably from about i to about 3 gram atoms. The Schiff base is blended with the metal Mannich complex simply by mixing therewith as an ambient temperature. Schiff bases of the type set forth above are known to the art and are generally commercially available. The metal Mannich complexes of the present inven

tion in combination with the Schiff base are often pre pared as a concentrate for later addition to the fuel. When utilized as a concentrate, the concentrate solution may also contain dispersants and substantially inert organic liquid diluents known to the art and to the liter ature. Examples of suitable dispersants include succini mides and the like. Suitable inert organic liquid diluents which generally do not react with the metal Mannich complex and/or Schiff base include various aliphatic and aromatic hydrocarbons such as naphthenic stocks, kerosene, textile spirits, benzene, toluene, xylene, alco hols such as isopropanol, n-butanol, isobutanol and 2-ethylhexanol, ether such as ethylene or diethylene cycloalkyl mono- or diethyl ether, mineral oil, synthetic oils and the like. Preferred diluents include mineral oil and aromatic naphtha. Although other additives can be utilized in the concentrate, the above additives are de sired. The amount of the metal Mannich complex with the Schiff base utilized in the concentrate is generally from about 10 to 99 weight percent with about 25 to about 75 weight percent being preferred. The metal Mannich complex with the Schiff base is

generally utilized as an additive for various fuel compo sitions. Such fuel compositions have varying boiling ranges, viscosities, cloud and pour points, etc., accord ing to their end use as is well known to those skilled in the art. Among such fuels are those commonly known as diesel fuels, distillate fuels, heating oils, residual fuels, bunker fuels, and the like. The properties of such fuels are well known to the art as illustrated, for example, by ASTM Specifications D 396-73. As noted above, a pre ferred use is in association with diesel fuels wherein good stability is achieved with reduced ignition temper atures of soot. The amount of reaction product of the present invention with the Schiff base in such fuels is from about one part to about 500 parts by weight of metal per one million parts by weight of said fuel and more desirably from about 15 parts to about 200 parts by weight. The following examples describe speci?c prepara

tions of compounds of the present invention.

EXAMPLE 1

A l2-liter, 4-neck ?ask with mechanical stirrer, ther mowell, thermometer, nitrogen sparge, H-trap, and condenser is charged with dodecyl phenol (3240 grams), hydro-re?ned naphthenyl oil (2772 grams) and ethanolamine (380 ml.). The mixture is stirred and heated to 72° C. and paraformaldehyde (372 grams) is

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rapidly charged thereto. The reaction temperature is increased to a maximum of 147° C. over a 3-hour period while sparging out water with nitrogen. A total of 218 m1. of water is collected versus a theoretical amount of 230 ml. At 25° C., Cu2(OH)2CO3 (663 grams) is then charged to the ?ask. The solution is warmed to 63° C. and aqueous ammonia (782 ml.) is added. The reactants are warmed while sparging out water (N; at 1.0 SCFH). The maximum temperature achieved over a period of 8.5 hours is 122° C. The amount of water collected is 648 -ml. theoretical amount of 662. The reactants are then cooled and ?ltered and the desired product ob tained. Yield is 6593 grams versus a theoretical amount of 6930 grams, that is, 95%.

EXAMPLE 2

A 12-liter, 4-neck ?ask equipped with a mechanical stirrer, thermowell, thermometer, nitrogen sparge, H trap, and condenser is charged with dodecyl phenol (3240 grams), an aromatic low boiling naphthenic sol vent (2500 grams) and ethanolamine (362 ml.). The reactants are stirred and heated to 70° C. and paraform aldehyde (372 grams) is charged rapidly to the solution. The solution is gradually heated while sparging with nitrogen. Maximum reaction temperature reached is 137° C. over a 5-hour period. 230 ml. of aqueous solu tion is collected. The reaction mixture is cooled to 30° C. and charged with aqueous ammonia (391 ml.). With the heat source shut off, Cu2(OI-I)2CO3 (663 grams) is gradually added over a 30-minute period. During the Cu2(OI-I)2CO3 addition, the reaction gives an exotherm of about 30°—47° C. The reaction temperature is then increased to about 70° C. with additional aqueous am monia (95 ml.) being rapidly charged. The solution temperature is gradually increased to collect water in the trap over a 14.5-hour period with a maximum tem perature of about 121° C. A total of 536 ml. of water is collected versus a theoretical amount of 537 ml. The solution is cooled and ?ltered. A yield of 93% is achieved.

EXAMPLE 3

A 2-1iter, 4-neck ?ask equipped with a mechanical stirrer, nitrogen sparge, H-trap, condenser and addition funnel is charged with 928 grams of a Mannich material as prepared in Example 1. The solution is heated to about 55° C. and Cu2(OH)2CO3 is charged to the ?ask (no CO2 evolution). When the temperature reached 60° C., aqueous ammonia is added over a lS-minute period. The temperature is gradually increased to a maximum of 120° C. over a 5-hour period while sparging. A total of 85 ml. of water is collected in the trap versus a theo retical amount 88 ml. The reaction product is ?ltered and a yield of 90% is achieved.

EXAMPLE 4

A 2-liter, 4-neck ?ask equipped with mechanical stir rer, thermowell, H-trap and condenser is charged with dodecyl phenol (900 grams), mixed xylenes (300 grams) and ethanolamine (105 grams). The mixture is stirred and heated to 70° C. and paraformaldehyde is added rapidly to the reaction. The reaction is then heated to 150° C. and water is removed through the H-trap. After the water is collected, the reaction is cooled to 120° C. and ?ltered. The ?ltrate is the Mannich. A l-liter, 4-neck ?ask equipped with thermowell,

mechanical stirrer, H-trap, and condenser is charged with basic copper carbonate (50 grams), isopropyl alco

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10 hol (200 milliliters) and ammonium hydroxide (100 mil liliters). This mixture is heated to 60° C. and 353 grams of the above Mannich material is added to the ?ask. The reaction is heated to re?ux the solvents and held for 3 hours. The material is then stripped of solvents and water at 135° C. with an aspirator vacuum of 18 mm. Hg. During the stripping the reaction is diluted with a naphthenic oil (220 grams). The ?ask contents are ?l tered and a yield of 92% is obtained; 481 grams versus a theoretical yield of 523 grams.

EXAMPLE 5

A 2-liter, 4-neck ?ask equipped with a mechanical stirrer, thermowell, H-trap and condenser is charged with dodecylphenol (900 grams), mixed xylenes (300 grams) and 50% aqueous NaOH (1 gram). The reaction is heated while stirring to 60° C. and charged with 53 grams paraformaldehyde. The ?ask is then heated to 110° C. for 1 hour until all paraformaldehyde is reacted. The material is further heated to 150° C. and H20 is removed. Formic acid is then added to neutralize the NaOH catalyst. Reaction is cooled to 60° C. and dieth anolamine and paraformaldehyde is charged succes sively. After addition is completed, the reaction is heated to a maximum of 135° C. and water is collected in the H-trap. When the reaction is completed, the ma terial is cooled and ?ltered. The ?ltrate is the desired Mannich material. ,

In a 1-liter, 4-neck ?ask equipped with mechanical stirrer, thermowell and condenser, basic copper carbon ate (50 grams), isopropyl alcohol (200 milliliters) and ammonium hydroxide (150 milliliters) is charged. This solution is heated to 38° C. and 425 grams of the above Mannich material is added to the stirring reaction. The Mannich is re?uxed for 5 hours and then solvents, water and ammonium hydroxide are removed by stripped with aspirator vacuum (21 mm. Hg.) at 120° C. The reaction is diluted with naphthenic oil (300 grams) dur ing stripping. The reaction is then cooled and ?ltered and 723 grams of product is obtained out of a theory of 752 grams. The yield is 96%. The Schiff base is added thereto simply by blending it

therewith as at ambient temperatures. In some in stances, the Schiff base is not soluble with the reaction product. In these situations, the Schiff base is usually independently added to the fuel.

Various reaction products prepared in the manner as set forth above were made and tested. A 1983 General Motors Cutlass Ciera 4.3-liter V-6 diesel engine on a chassie dynamometer is utilized. The conditions simu lated are 40 m.p.h., a road load of 1.5, a test duration of 3 hours and fuel rate of 1.3 grams per second. A Cor ning ?lter trap product code 433347-3 is attached to the exhaust system of the engine. After the test, the particu lates are removed from the trap by sawing one inch off the exhaust end of the trap. The particles are collected by pushing the same from the trap inlet end towards the exhaust end. The particulates are then transferred to a thermal gravimetric analyzer for determination of igni tion temperature. The particulate ignition temperature response is as set forth in the following table.

Particulate Ignition Temperature Response Concentration Ignition Temperature

Metallic ppm, wt/wt Reduction °C.

Cu (A)" 123 25s

4,816,038 11

-continued Particulate Ignition Temperature Response

Concentration Ignition Temperature Metallic ppm, wt/wt Reduction °C.

Cu (8)" 123 250

'Dodecylphenol/(CH2O),/Ethanolamine (2:2:1)m/Cu2(OI-I)2CO3/NH3(ag) (IN:~ lCuzZN) -

"Cu(A)/N-N’—disalicylidene-l,2-propane diamine

The fuel utilized was a conventional fuel such as DDR-366 distributed by the Howell Hydrocarbon Company and the various reactants were made in the manner as set forth in Example 2. As apparent from the above table, signi?cant ignition

temperature reductions were obtained, especially with copper-containing compounds.

General Screening tests'were made as for example a 90-minute, 300‘ F. fuel oil accelerated stability test. This test is generally an accepted test known to the art and is also known as a Sante Fe Railroad Test, Union Paci?c Railroad Test, A Nalco or a DuPont Test. The test purpose, outlined, materials and procedure are as fol lows:

Purpose: To determine the resistance of fuel oil to degradation

in storage. Heat and exposure to air are substituted for storage time. The effectiveness of fuel stabilizers can be evaluated by this method.

Outline: A 50 ml. portion of the fuel oil in a test tube is heated

at 300° F., and the ASTM color is determined before and after the test. In addition, the fuel i ?ltered through ?lter paper, and the stain is compared with standard stains.

Materials: 1. 3X20 cm. Pyrex test tubes 2. Oil bath set at 300° F.—Dow Corning DC 200

Fluid stirred and themostatically controlled 3. Suction ?ask 4. No. 1 Whatman ?lter pads (4.2 cm. dia.) 5. Heptane or Iso-octane 6. Colorimeter (ASTM) 7.1 Standard set of ?lter pads (Nalco rating system,

0.20) 8. Millipore ?lter apparatus Procedure:

1. Some fuels are tested on an “as received” basis and some are pre?ltered through Whatman No. 1 ?lter paper on the day of the test.

2. All fuels are saturated with air by gentle bubbling for 2 minutes just before the start of the test.

3. The test fuel is placed in a 3 X20 cm. Pyrex test tube and the original color and ?lter pad ratings of the sample are determined. a. The ASTM color is determined. b. The filter pad rating is determined by vacuum

?ltration of a 50 ml. sample of the oil through two No. 1 Whatman ?lter papers. Suction is applied only after the sample is in the Millipore ?lter. Two ?lter papers are used so that the sediment being collected is uniformly dispersed on the top paper.

4. The ?lter pad is then washed with heptane or iso octane, air-dried, and the top paper is rated by com paring it to the standard set of ?lter pads numbered 1 to 20. The bottom paper is discarded.

5. After the preliminary work is completed, 50 ml. of each treated oil sample in 3X20 cm. test tubes is

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12 placed in a 300“ F. oil bath. An untreated (blank) sample is to be included.

6. After 90 minutes (or 5 hours if speci?ed) the samples are removed from the oil bath and are allowed to cool to room temperature for 1 hour in the dark.

7. When cool, each sample test tube is wiped dry and the color is determined. Each 50 ml. sample is then ?ltered as above (3b), and rated (4).

8. The ?nal color and ‘filter pad ratings are compared to the original color and ?lter pad ratings to evaluate the degrees of degradation.

9. The stain on the inside of the tube is recorded as None, Light, Medium or Heavy. Various compositions were made and tested and the

results thereof are set forth within Table A. Table A relates to a test wherein one of the composi

tions contained a Schiff base.

TABLE A

Base Fuel = No. 2 Fuel Oil 90-min/ 300° F. Stability

ASTM D-2274

Treatment ASTM Color Tot. Insol. Level/ppm Additive Initial Final mg/ 100 ml.

A None L2.0 1.2.5 0.32 B 513 Cu Cem All L3.0 L5.5 (10%)‘

(12% Cu)(Mooney) C 1404 Copper Mannich L3.0 L3.5 (30%)‘

Compound of Ex. 3 D 1404 Copper Mannich L3.5 L5.0 0.25

Compound of Ex. 3 366 N,N'-disalicyl idene-l,2-propane diamine

‘Percent of sample filtered before pluggage.

As apparent from Table A, compound B caused se vere degradation of the base fuel. The copper Mannich compound of the present invention when added pro duced a stable fuel, compound C. A further improve ment is achieved when a Schiff base is utilized, com pound D.

Table B relates to a 13-week storage stability test.

TABLE B 110“ F./ 13-week Storage Stability

ASTM D-1500 ASTM D-2274 Color Ratings Insol. Residue

Final Rating Residue l3-wks. mg/lOO ml.

L2.5 0.23 L5.0 68.41

Initial

L2.0 L3.0

Additive Treatment

AA No Additive BB Copper Cem-All

(Mooney) 0.2 g. Cu/Gal. 1234 ppm Copper Mannich Compound of Ex. 4 1493 ppm Copper Mannich Compound of Ex. 5 1234 ppm Copper Mannich Compound of Ex. 4. 366 ppm N—-N’—dis alicyl idene-l,2 propanediamine 1493 ppm Copper Mannich of Ex. 5 366 ppm N,N'--dis alicyl idene-l,2 propanediamine

CC L3.0 L5.0 3.12

DD Ll.5 L4.0 10.78

EE L4.5 L5.5 0.76

FF L4.5 L5.5 0.75

4,816,038 13

As apparent from Table B, compound BB caused sever degradation of the base fuel. The copper Mannich compound CC and DD improved fuel stability. Com pounds EE and FF further improved fuel stability. While in accordance with the patent statutes, a best 5

mode of preferred embodiment has been set forth in detail, the scope of the invention is not limited thereby, but rather by the scope of the attached claims. What is claimed is: 1. The reaction product of: 10 (A) a compound having the formula

1'‘. (R‘)n—AY_(XH)m 15

wherein Ar is an aromatic group or a coupled aro matic group, wherein m is l, 2 or 3, wherein n is an integer from 1 to 4, wherein R1 independently, is hydrogen or a hydrocarbyl having from 1 to about 100 carbon atoms, wherein R° is H, amino or car boxyl, and wherein X is O, S, or both when m is 2 or greater;

(B) a compound having the formula

25

or a precursor thereof wherein R2 and R3, indepen dently, is hydrogen, a hydrocarbon having from 1 to about 18 carbon atoms, or wherein R3 is a car bonyl or a carboxyl-containing hydrocarbon hav ing from 1 to 18 carbon atoms;

(C) a hydroxyl-containing amine compound, a thiol containing amine compound, or a hydroxyl-thiol- 35 containing amine compound containing from about 1 to about 10 primary or secondary amine groups therein, from about 1 to about 10 thiol groups therein, and from about 1 to about 10 hydroxyl groups therein; with at least one

(D) transition metal containing agent in the molar ratio of A:B:C:D of from about 0.5-6:O.5-6:1.0:0 5-2 when C is a primary amine compound and from about 0.2—2:0.2-2:1.0:0.2—2 when C is a sec ondary amine compound, and 45

(E) an effective amount of a Schiff base of the for mula:

R10 50 I

(Rs)p N=C—@'(0H)r (R9); I 55

wherein p is 1 or 2, wherein R8 is hydrogen, a hydrocarbyl having from 1 to about 20 carbon atoms, or an alkyl amine, diamine or polyamine haing from 1 to 20 carbon atoms, wherein s is 1 or 60 2, wherein R9, independently, is hydrogen or a hydrocarbyl having from 1 to about 20 carbon atoms, wherein r is 1 or 2, wherein R10 is hydrogen or lower alkyl, and wherein t is l to 6.

2. The product of claim 1 wherein R1 of said (A) 65 compound is hydrogen, or an alkyl having from 1 to about 30 carbon atoms, a cycloalkyl having from 4 to about 10 carbon atoms, an alkenyl having from 2 to

20

40

14 about 30 carbon atoms, an aromatic or an alkyl-sub stituted aromatic having from about 7 to about 30 car bon atoms or an aromatic-substituted alkyl having from about 7 to about 30 carbon atoms, and wherein said Ar is coupled with a coupling agent and wherein said cou pling agent of said coupled Ar group is O, S, NH or a lower alkylene.

3. The product according to claim 2 wherein said (C) compound is said hydroxyl-containing amine having from 1 to about 10 hydroxyl groups therein and from 1 to about 10 amine groups therein, or said hydroxyl-thi ol-containing amine having from 1 to about 10 hydroxyl groups therein, from 1 to about 10 thiol groups therein and from 1 to about 10 amine groups therein; wherein R2 and R3 of said (B) compound, independently, is hy drogen, an alkyl phenyl or an alkyl-substituted phenyl wherein said alkyl contains from 1 to 18 carbon atoms or R3 is a carboxyl-containing alkyl wherein said alkyl has from 1 to 18 carbon atoms.

4. The product of claim- 3 wherein said (C) hydroxyl containing amine is a compound having the formula

or a compound having the formula

or a cyclohydrocarbyl hydroxyl-containing amine hav ing from 3 to 20 carbon atoms wherein R4 is a hydrocar bylene having from 1 to about 20 carbon atoms, wherein R5 is hydrogen or a hydrocarbyl having from 1 to about 20 carbon atoms, wherein o is an integer of from 1 to 10, wherein R6 is hydrogen, a hydroxyl con taining hydrocarbyl having from 1 to about 20 carbon atoms, a hydrocarbyl primary amine having from '1 to about 20 carbon atoms, or a hydrocarbyl polyamine having from 1 to about 20 carbon atoms, and wherein the total number of R5 and R6 carbon atoms is 24 or less.

5. The product of claim 4 wherein Ar of said (A) compound is phenyl, wherein m is l or 2, wherein n is 1 or 2, wherein n is l or 2, wherein R“ is H, wherein R1 is an alkyl having from about 7 to about 20 carbon atoms, a cycloalkyl having from about 5 to about 7 carbon atoms, an alkenyl having from about 8 to about 20 carbon atoms, or an alkyl-substituted aromatic hav ing from 7 to about 12 carbon atoms, wherein said (D) metal of said transition metal-containing agent is cop per, iron, zinc, manganese, or combinations thereof.

6. The metal product of claim 5 wherein R4 of said (C) hydroxyl-containing amine is an alkylene having from 2 to about 6 carbon atoms, wherein R5 is hydrogen or an alkyl having from 1 to about 20 carbon atoms, and R6 is hydrogen, a hydroxyl-containing alkyl having from 1 to about 20 carbon atoms, an alkyl primary amine having from to about 20 carbon atoms, or an alkyl polyamine having from 1 to about 20 carbon atoms, and wherein said cyclohydrocarbyl hydroxyl containing amine is a cycloalkyl hydroxyl containing amine having from 3 to about 6 carbon atoms.

7. The product of claim 6 wherein m of of said (A) compound is 1, wherein n is l or 2, wherein R1 is an alkyl having from about 7 to about 20 carbon atoms, and wherein X is O, and wherein R2 and R3 of said (B) compound is hydrogen.

4,816,038 15

8. The product of claim 7 wherein R4 of said (C) hydroxyl-containing amine is an alkylene having 2 or 3 carbon atoms, wherein R5 is hydrogen, or an alkyl hav ing 1 or 2 carbon atoms, wherein o is l, and wherein R6 is a hydroxyl-containing alkyl having 2 or 3 carbon atoms, an alkyl primary amine having 2 or 3 carbon atoms, or an alkyl polyamine having 2 or 3 carbon atoms.

9. The product of claim>8 wherein said (D) metal of said transition metal-containing agent is copper, and said (C) hydroxyl-containing amine compound is etha nolamine or diethanolamine.

10. The product of claim 1 wherein the amount of said Schiff base (E) is from about 0 to about 4 gram atoms of nitrogen as imine groups per gram atom of said metal in said reaction product.

11. The product of claim 10 wherein the amount of said Schiff base (E) if from about i to about 3 gram atoms of nitrogen as imine groups per gram atom of said metal in said reaction product, wherein p is 1, wherein R8 is a primary alkyl amine having from 1 to 20 carbon atoms, wherein s is 1, wherein R9 is hydrogen or an alkyl having from 1 to about 6 carbon atoms, wherein R10 is hydrogen, wherein r is 1, and wherein t is 2.

12. A fuel composition comprising a major amount of a fuel and a minor amount of the product of claim 1.

13. A fuel composition comprising a major amount of a fuel and a minor amount of the product of claim 8.

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16 14. A fuel additive for reducing the ignition tempera

ture of soot from an exhaust gas comprising the compo sition of claim 1.

15. A fuel additive for reducing the ignition tempera ture of soot from an exhaust gas comprising the compo sition of claim 7.

16. A fuel additive for reducing the ignition tempera ture of soot from an exhaust gas comprising the compo sition of claim 10.

17. A fuel additive concentrate comprising: an or ganic solvent, and from about 10% to about 99% by' weight of the composition of claim 1.

18. A fuel additive concentrate comprising: an or ganic solvent, and from about 10% to about 99% by weight of the composition of claim 3.

19. A fuel additive concentrate comprising: an or ganic solvent, and from about 10% to about 99% by weight of the composition of claim 4.

20. A fuel additive concentrate comprising: an or ganic solvent, and from about 10% to about 99% by weight of the composition of claim 7.

21. A fuel additive concentrate comprising: an or ganic solvent, and from about 10% to about 99% by weight of the composition of claim 9.

22. A fuel additive concentrate comprising: an or ganic solvent, and from about 10% to about 99% by weight of the composition of claim 10.

23. A fuel additive concentrate comprising: an or ganic solvent, and from about 10% to about 99% by weight of the composition of claim 11.

IR * * * *